Shaun Bartlett netted a brace to make it an unhappy day for Tottenham's caretaker boss Martin Jol.
The Dutchman was asked to take charge of first-team affairs following the shock resignation of Jacques Santini on Friday night.
The former France coach cited personal reasons for his decision to leave the North-London club, but his timing could not have been worse just 24 hours before the game.
The Tottenham players were left shell-shocked by the decision and it clearly showed as they struggled to contain a rampant Charlton side for who Danny Murphy dominated.
The visitors opened the scoring after just 17 minutes when the impressive Jerome Thomas picked out Bartlett with a cross and the South African volleyed the ball beyond Paul Robinson in the Spurs goal.
Tottenham almost equalised in the 35th minute when Robbie Keane's cross found Ledley King in the box, but his header went just wide of the far post.
Two minutes later Freddie Kanoute made space for himself but his shot flew high over the crossbar.
The home side were made to pay for those missed opportunities when, after 38 minutes, Luke Young's superb ball into the box fell perfectly for Bartlett, who planted a diving header past Robinson.
Tottenham's luck went from bad to worse on 49 minutes when Thomas' shot hit King's heel and flew into the back of the net to give Charlton a comfortable three-goal lead.
Keane tried to get the home side back in to the game after 62 minutes when he found space inside the box, but saw his shot well saved by Dean Kiely in the Charlton goal.
Jol tried to change things around for the home side when he introduced Michael Carrick for the ineffective Jamie Rednapp, much to the delight of the home crowd.
It almost paid dividends straight away when Jermain Defoe weaved and turned inside the box - but he fired just over the bar.
The turning point of the game came after 67 minutes as Bartlett turned from hero to villain when he was a sent off for handling the ball on the line.
Reto Ziegler's shot seemed to heading for the back of the net until the South African international made a superb block to stop the ball crossing the line.
Referee Neale Barry had no option but send him off and Keane made no mistake from the penalty spot.
The goal fired Spurs into life and Noureddine Naybet was unlucky to see his header fly just over the bar.
Tottenham made a real game of it on 79 minutes when Keane's ball found Defoe. The England star turned superbly and fired an unstoppable shot past Kiely into the corner of the net.
The home side did everything in last ten minutes to try and snatch an equaliser but Charlton held firm and managed to secure their first Premiership away win of the season.
Man of the Match: Jerome Thomas The former Arsenal trainee was a constant threat to Spurs and created the opener before notching the third.